电感耦合等离子体原子发射光谱法测定镍基高温合金中铬、钛、铌、铝、铁、硼的含量

在对各元素的分析谱线的选择及基体元素镍对相关元素测定的干扰作了系统研究的基础上,提出用电感耦合等离子体原子发射光谱法(ICP-AES)同时测定镍基高温合金中铬、钛、铌、铝、铁及硼6种合金元素的方法。上述6种元素的检出限(3s/k)在0.006 9~0.13 mg.L-1范围内。取GH 33镍基高温标准样品按所提出方法分析,测定值与标准值相互一致,测得相对标准偏差值(n=10)均小于1.5%。在基体镍溶液中加入各被测元素的标准溶液做回收试验,上述6种元素的回收率在98.3%~101.0%之间。为对此方法的准确性作进一步考核,对GH 4145高温镍基合金样品进行分析,各元素的测定值与国家标准方法的测定值相符合。     

电感耦合等离子体发射光谱（ICP-OES）法测定镍-铬基高温合金GH4133B中铝、铌、钛、铬、铁

GH4133B是Ni-Cr基沉淀硬化型变形高温合金,近年来我国还没有适宜的国家检测标准,基于此对样品主要元素含量准确测定方法进行了研究和探讨。采用盐酸-硝酸体系对GH4133B镍基高温合金进行溶解,确定了盐酸和硝酸比列为8∶3,混合酸用量为11 mL,用ICP-OES法快速准确地对GH4133B镍基高温合金中铝、铌、钛、铬、铁元素含量进行测定;确定了各元素分析谱线为Al 396.152nm、Nb 309.417nm、Ti 334.941nm、Cr 267.716nm、Fe 238.204nm;建立了校准工作曲线,各元素线性相关系数均在0.999以上;优化仪器参数,消除基体干扰,测定了方法检出限,各元素检出限均小于0.003%,各元素测定结果的RSD/%在0.26%～0.47%(n=7),加标回收率在99.4%～105%。有效解决了GH4133B镍基高温合金快速有效溶解及准确测定问题。     

高频红外碳硫仪快速测定镍基高温合金中碳、硫

建立了高频红外碳硫仪快速测定镍基高温合金中碳、硫的方法。通过对样品称样量、助熔剂的选择及加入量等方面考察,确定了镍基高温合金样品的最佳测定条件。结果表明,称取样品、钨锡助熔剂各1.0 g左右时,测定效果最佳,碳和硫的方法检出限分别为0.000 11%、0.000 03%,方法测定下限分别为0.000 44%、0.000 12%,测定值的相对标准偏差为0.51%～2.38%(n=6),相对误差均小于5%。该方法适合于镍基高温合金中碳、硫含量的测定。     

镍基高温合金元素分析方法研究进展

对近10年来镍基高温合金分析方法标准的修订情况以及分析方法研究方面的进展进行综述,主要包括我国国家标准和美国ASTM标准的修订情况,以及原子吸收光谱法、原子发射光谱法、电感耦合等离子体质谱法、同位素稀释质谱法等分析方法的特点等的归纳总结,对各方法的优缺点和适用范围进行了比较。我国目前还没有相应的国家标准,现行分析方法陈旧、繁琐,具有一定的局限性,制约着我国高温合金材料的发展。综合不同测试技术的特点,建立一套高灵敏度,高准确度,低检出限,快速简便,自动化的镍基高温合金元素分析方法体系,从而实现镍基高温合金中元素分析水平的飞跃。     

X射线荧光光谱法测定镍基高温合金中合金组分的通用工作曲线的制作——基本参数(FP)法虚拟合成标准样品的应用

应用基本参数(FP)法虚拟合成标样制作了X射线荧光光谱法(XRFS)测定不同类型的镍基高温合金中18种合金元素和4种杂质元素的通用工作曲线。选择了最佳的仪器工作条件和合理的待测元素的分析线系,测定了9种元素受共存元素分析线重叠干扰的校正系数,用瑞利散射线扣除背景及通道材料的影响。在设定虚拟合成标样中各元素的含量,并算得在此设定值下的荧光强度后,用FP法计算各元素在其定值下的最终强度,从而完成了FP法工作曲线。应用此虚拟合成单标工作曲线对多种标准样品进行测定,证明该工作曲线可通用于各种类型的镍基高温合金的分析。     

镍释放量标准物质的研制

研制了镍释放量标准样品。以铜粉、锌粉、镍粉为原料,通过熔炼炉熔炼及模具加工制备镍释放量标准物质,采用能量色散荧光光谱法(EDX)确认镍含量。样品分装成200份,采用电感耦合等离子体光谱法(ICP)进行均匀性、稳定性检验和定值分析。从样品中随机抽取15份进行均匀性检验,经F检验表明在95%的置信区间范围内样品均匀性良好;在常温条件下,经过12个月长期试验稳定性考察,统计值t均小于临界值2.571,结果表明样品稳定性良好。镍释放量定值结果为1.121μg/(cm~2·week)。对镍释放量定值结果进行了不确定度评估,扩展不确定度为0.300μg/(cm~2·week)(k=1.96)。该镍释放量标准物质符合检测需要,可用于合金产品镍释放量检测的方法校正和质量控制。     

火焰原子吸收光谱法测定镍基高温合金中的镉

采用火焰原子吸收光谱法测定镍基高温合金中的镉,样品以硝酸-氢氟酸-水混合溶液(1+1+1)前处理,选择Cd 228.8 nm为分析线进行测定,并通过标准加入法校正基体效应。考察了消解酸的选择,仪器工作参数的调整,基体和共存离子对镉测定的影响。结果表明,镍基高温合金中镉的检出限为0.088μg/g。加标回收率为94.1%~109%,结果的相对标准偏差(RSD,n=8)在0.54%~1.6%。方法操作简便、分析速度快、准确度好,适用于镉含量在0.0001%~0.001%的镍基高温合金中的测定。     

盐酸-硝酸体系溶解―ICP-OES法测定镍-铬基高温合金GH4133B中铝铌钛铬铁

GH4133B是Ni-Cr基沉淀硬化型变形高温合金,近年来我国还没有适宜的国家标准,基于此对样品主要元素含量准确测定方法进行了研究和探讨。采用盐酸-硝酸体系对GH4133B镍基高温合金进行溶解,确定了盐酸和硝酸比列为8:3,混合酸用量为11mL;采用ICP-OES法快速准确的对GH4133B镍基高温合金中铝、铌、钛、铬、铁元素含量进行测定;确定了各元素分析谱线为Al396.152nm、Nb309.417nm、Ti334.941nm、Cr267.716nm、Fe238.204nm;建立了校准工作曲线,各元素线性相关系数均在0.999以上;优化仪器参数消除基体干扰,测定了方法检出限,各元素检出限均小于0.003%,各元素测定结果的RSD/%在0.26%～0.47%之间(n=7),加标回收率在103.0％~104.5％之间。有效解决了GH4133B镍基高温合金快有效速溶解及准确测定问题。     

火焰原子吸收光谱法测定镍基高温合金中的镉

采用火焰原子吸收光谱法测定镍基高温合金中的镉,样品以硝酸-氢氟酸-水混合溶液(1+1+1)前处理,选择Cd 228.8nm为分析线进行测定,并通过标准加入法校正基体效应。考察了消解酸的选择,仪器工作参数的调整,基体和共存离子对镉测定的影响。结果表明,镍基高温合金中镉的检出限为0.088μg/g。加标回收率为94.1%～109%,结果的相对标准偏差(RSD,n=8)在0.54%～1.6%。方法操作简便、分析速度快、准确度好,适用于镉含量在0.0001%～0.001%的镍基高温合金中的测定。     

高分辨电感耦合等离子体质谱法测定镍基单晶高温合金中36种痕量元素

基于高分辨电感耦合等离子体质谱法(HR-ICP-MS)的质谱干扰消除技术,对镍基单晶高温合金中36种痕量元素检测的质谱条件、基体干扰、质谱干扰与同位素选择进行了研究。取样品0.100 0 g,用体积比为3∶1的盐酸-硝酸混合酸10 mL、氢氟酸1 mL溶解,用水定容至250 mL。通过复杂基体质谱干扰计算判定、共存元素干扰消除,确定了待测元素的同位素和分辨模式,将镍基单晶高温合金中痕量元素准确测定的元素种类确定为36种。采用标准加入法进行定量分析,36种痕量元素的检出限(3s)为0.004～6.000μg·L^-1。方法用于分析国际标准物质,得到的测定值与认定值基本一致。方法用于镍基单晶高温合金样品分析,36种痕量元素的检出量为0.000 001 0%～0.018%。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Thermodynamics of the formation of oxosulfides of rare-earth elements

The enthalpies of solution of several oxosulfides of rare-earth elements and the high-temperature enthalpies of oxosulfides and oxosulfates of lanthanum and yttrium were measured using solution calorimetry and high-temperature microcalorimetry techniques. Standard enthalpies of formation and some thermodynamic properties of oxosulfides and oxosulfates were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2 pp. 294–297, February, 1997.     

探究“铁的锈蚀条件”实验创新设计

设计了铁的锈蚀实验,说明了铁钉的处理方法,增加了温度、酸、碱的影响条件,实现了铁跟蒸馏水及空气中氧气快速反应而生锈,使实验在5 min左右就能够得到准确的结果。